US8941089B2 - Resistive switching devices and methods of formation thereof - Google Patents
Resistive switching devices and methods of formation thereof Download PDFInfo
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- US8941089B2 US8941089B2 US13/767,800 US201313767800A US8941089B2 US 8941089 B2 US8941089 B2 US 8941089B2 US 201313767800 A US201313767800 A US 201313767800A US 8941089 B2 US8941089 B2 US 8941089B2
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- H10N70/20—Multistable switching devices, e.g. memristors
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- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
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- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
- H10N70/235—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect between different crystalline phases, e.g. cubic and hexagonal
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- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
- H10N70/245—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies the species being metal cations, e.g. programmable metallization cells
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- H10N70/821—Device geometry
- H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
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- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
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- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8825—Selenides, e.g. GeSe
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- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
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- H10N70/883—Oxides or nitrides
- H10N70/8836—Complex metal oxides, e.g. perovskites, spinels
Definitions
- the present invention relates generally to electronic devices, and more particularly to resistive switching devices and methods of formation thereof.
- Flash memory is the mainstream non-volatile memory in today's market.
- Flash memory has a number of limitations that is posing a significant threat to continued advancement of memory technology.
- Current stand alone and embedded memory technologies suffer many drawbacks due to the extreme demands of scaling dictated by Moore's law.
- MRAM magnetic storage random access memory
- FeRAM ferroelectric RAM
- PCRAM phase change RAM
- RRAM resistive RAM
- ionic memories including programmable metallization cell (PMC) or conductive bridging random access memory (CBRAM).
- PMC programmable metallization cell
- CBRAM conductive bridging random access memory
- CBRAM Conductive Bridging Random Access Memory
- NVM Non-volatile memories
- CBRAM technology offers simple integration and scalable operational conditions.
- CBRAM may be integrated into copper and aluminum back end logic CMOS processes with minimal number of added masks with no adverse impact to the CMOS technology.
- CBRAM offers promising operation parametrics which are increasingly difficult to achieve with other types of memories such as low operational voltage ( ⁇ 1 V), low operational current (1 A), and ultrafast switching ( ⁇ 100 ns). These unique features make CBRAM technology an ideal candidate for embedded applications.
- CBRAM technology is also known by other names such as programmable metallization cell (PMC) solid electrolyte memory, nano-ionic resistive memory, electrochemical memory (ECM).
- PMC programmable metallization cell
- ECM electrochemical memory
- CBRAM memory devices utilize solid state electrochemistry to modulate the resistance of certain materials known as solid electrolytes by reversibly creating a nanoscale conductive link inside them when biased by small voltages.
- devices using this technology may be composed of a thin film of silver doped chalcogenide or oxide glass sandwiched between a silver anode and an inert cathode. Under the influence of an electric field the electron current from the cathode reduces an equivalent number of Ag-ions as injected from the anode and a metal-rich electrodeposit is thereby formed in the electrolyte. The magnitude and duration of the ion current determines the amount of Ag deposited and hence the conductivity of the pathway.
- the electrodeposit is electrically neutral and stable; however, the formation process can be reversed by applying a bias with opposite polarity.
- the basic storage element consists of an access transistor and a programmable resistor (1T-1R) (similar to the DRAM one transistor and one capacitor cell).
- a resistive switching device comprises an opening disposed within a first dielectric layer, a conductive barrier layer disposed on sidewalls of the opening, a fill material comprising an inert material filling the opening.
- a solid electrolyte layer is disposed over the opening. The solid electrolyte contacts the fill material but not the conductive barrier layer.
- a top electrode is disposed over the solid electrolyte.
- a method of forming a resistive switching device comprises forming an opening within a first dielectric layer over a substrate, forming a conductive barrier layer on sidewalls of the opening, and filling the opening with a fill material comprising an inert material.
- a solid electrolyte layer is formed over the opening. The solid electrolyte contacts the fill material but not the conductive barrier layer.
- a top electrode is formed over the solid electrolyte.
- FIG. 1 illustrates a cross-sectional view of a prior art conductive bridging random access memory device
- FIG. 2 which includes FIGS. 2A-2D , illustrates a resistive switching device during various stages of fabrication in accordance with an embodiment of the invention
- FIG. 3 which includes FIGS. 3A and 3B , illustrates embodiments in which one of the top surface of the bottom electrode of the resistive switching device is deactivated or may not participate in the electrical operation of the device;
- FIG. 4 illustrates an alternative embodiment of a resistive switching device comprising a barrier layer and a switching layer
- FIG. 5 illustrates a resistive switching device in accordance with an alternative embodiment of the present invention
- FIG. 6 which includes FIGS. 6A-6D , illustrates a resistive switching device during various states of fabrication, wherein the top surfaces are selectively modified, wherein FIGS. 6C and 6D illustrate alternative embodiments;
- FIG. 7 which includes FIGS. 7A-7D , illustrates an alternative embodiment of the invention for forming the structure illustrated in FIG. 2 ;
- FIG. 8 which includes FIGS. 8A-8H , illustrates a resistive switching device during fabrication in accordance with various embodiments of the invention.
- FIG. 9 which includes FIGS. 9A and 9B , describes an alternative resistive switching device during various stages of fabrication in accordance with an embodiment of the invention.
- ionic switching devices such as programmable metallization cells (also called as conductive bridging memories, nanobridge memories, or electrolytic memories).
- the invention may also be applied, however, to other types of memories, particularly, to any two terminal resistive memory such as metal oxide memories and phase change memories.
- resistive switching such as processors, dynamically-reroutable electronics, optical switches, field-programmable gate arrays, and microfluidic valves as well as other nanoionic devices.
- FIG. 1 illustrates a cross-sectional view of a prior art CBRAM device.
- a metal line 10 is disposed within a first dielectric layer 20 .
- the CBRAM device comprises a bottom electrode, which is an inert electrode, a solid electrolyte 60 , a top electrode 70 .
- the inert electrode of the CBRAM device is embedded within a second dielectric layer 50 .
- the inert electrode is typically enclosed with a diffusion barrier/adhesion promoting layer. Accordingly, the inert electrode of the CBRAM device comprises a fill material 40 and a barrier layer 30 .
- the solid electrolyte 60 and the top electrode 70 may be formed over the solid electrolyte 60 .
- the device may have a partial or soft trigger above a region of the switching layer 60 above the barrier layer 30 relative to the fill material 40 .
- FIG. 2 A structural embodiment of a resistive switching device will be described using FIG. 2 (e.g., FIG. 2D ). Further structural embodiments will be described using FIGS. 3-5 , 7 D, 8 H, and 9 . Embodiments of fabricating the resistive switching devices will be described using FIGS. 2 , 5 - 9 .
- FIG. 2 which includes FIGS. 2A-2D , illustrates a resistive switching device during various stages of fabrication in accordance with an embodiment of the invention.
- resistive switching devices may be fabricated within metallization levels after forming the semiconductor regions within a substrate.
- resistive switching devices may be integrated with back-end-of-the-line processes.
- the illustrated resistive switching device is formed over the first and the second metal levels.
- the location of the resistive switching device within the metallization layers may be different.
- the lower metal levels are disposed within a dielectric layer, which may comprise a plurality of dielectric layers.
- FIG. 2 illustrates an example of having at least three metallization levels under the resistive switching devices.
- the resistive switching devices are disposed over a substrate 100 .
- the substrate 100 may comprise a bulk silicon wafer in one embodiment.
- the substrate 100 may comprise any suitable semiconductor, for example, within which the access device such as a transistor or diode is fabricated.
- Some examples of the substrate 100 include bulk mono-crystalline silicon substrate (or a layer grown thereon or otherwise formed therein), a layer of (110) silicon on a (100) silicon wafer, a layer of a silicon-on-insulator (SOI) wafer, or a layer of a germanium-on-insulator (GeOI) wafer.
- the substrate 100 may include wafers with epitaxial layers, for example, silicon epitaxial layer over a silicon bulk wafer, gallium nitride over silicon or gallium arsenide, and other hetero-epitaxial structures.
- the substrate 100 may undergo front end processing using conventional semiconductor processing.
- active device regions may be formed within the substrate 100 in various embodiments.
- the formation of active device regions may include forming transistor regions such as gate dielectric layers, gate electrode, source/drain regions, channel regions, and other associated structures such as isolation trench regions.
- doped regions 110 may be formed within the substrate 100 .
- the doped regions 110 may be source/drain regions of the transistors and may be formed using implantation and/or epitaxial process with further annealing.
- a suitable silicide metal is deposited over the doped regions 110 .
- the substrate 100 is then heated to about 500° C. to 700° C.
- the exposed doped regions 110 react with the silicide metal to form a layer of metal silicide. Any un-reacted silicide metal may be removed.
- the device undergoes back end of the line manufacturing, wherein, contacts are made to the semiconductor body and interconnected using metal lines and vias.
- Modern integrated circuits incorporate many layers of vertically stacked metal lines and vias (multilevel metallization) that interconnect the various components in the chip.
- a plurality of metallization layers are formed over the substrate 100 using conventional processing.
- the metallization layers may be formed using damascene, dual damascene processes in various embodiments.
- a first insulating layer 111 is formed above the substrate 100 .
- the first insulating layer 111 may be an oxide layer in one or more embodiments.
- the first insulating layer 111 may comprise an insulating layer suitable for inter level dielectric such as a deposited oxide.
- the first insulating layer 111 may comprise a plurality of layers in one or more embodiments.
- the first insulating layer 111 comprises insulating materials used in semiconductor manufacturing for inter-level dielectric (ILD) layers, such as SiO 2 , tetra ethyl oxysilane (TEOS), which is a form of silicon dioxide, fluorinated TEOS (FTEOS), doped glass (BPSG, PSG, BSG), organo silicate glass (OSG), fluorinated silicate glass (FSG), spin-on glass (SOG), SiN, and/or SiON.
- TEOS tetra ethyl oxysilane
- FTEOS fluorinated TEOS
- BPSG, PSG, BSG organo silicate glass
- FSG fluorinated silicate glass
- SOG spin-on glass
- SiN SiN
- SiON SiN
- SiON SiN
- SiON silicon oxide
- the first insulating layer 111 may comprise a thickness of about 500 nm or less, for example.
- the first insulating layer 111 may include
- An etch stop liner (not shown) may be deposited prior to the first insulating layer 111 over the substrate 100 .
- a nitride film e.g., silicon nitride
- silicon nitride may be deposited as an etch stop liner.
- Contact plugs 11 are disposed within the first insulating layer 111 and may be coupled to various regions of the substrate 100 .
- the contact plugs 11 within the first insulating layer 111 may be coupled to doped regions 110 of an access device.
- the doped regions 110 of the access device comprise source/drain regions.
- the contact plugs 11 may be coupled to the doped regions 110 through silicide regions in various embodiments.
- contact holes are formed in the first insulating layer 111 .
- photoresist (not shown) is deposited and patterned to mask off the non-exposed regions to the subsequent etch process.
- the first insulating layer 111 is then etched down to expose the underlying doped regions 110 using standard etch techniques such as a reactive ion etch.
- An optional conductive liner and a conductive material are then deposited using, for example, a chemical vapor deposition process (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD) process into the contact hole.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- ALD atomic layer deposition
- the contact plugs 11 may comprise tungsten and/or other contact materials such as copper, aluminum, Al—Cu—Si, other metals and combinations thereof. If the conductive material comprises tungsten, a bi-layer seed layer comprising CVD titanium nitride and silicon doped tungsten may be used in some embodiments. In some embodiments, the contact plugs 11 may be filled with copper.
- a second insulating layer 112 is deposited over the first insulating layer 111 .
- the second insulating layer 112 may comprise a similar material as the first insulating layer 111 in one embodiment.
- Another photoresist is deposited, patterned, and openings for the metal lines are formed.
- the first metal lines 12 may be formed within the openings for the metal lines, using, e.g., a single damascene process in one embodiment.
- the first metal lines 12 in the second insulating layer 112 may be coupled to the contact plugs 11 .
- the first metal lines 12 may comprise copper in one or more embodiments.
- the first metal lines 12 may comprise other conductive materials such as aluminum.
- the first metal lines 12 may include a diffusion barrier and other conductive liners.
- a third insulating layer 121 is deposited over the first insulating layer 111 .
- the third insulating layer 121 is disposed above the first and the second insulating layers 111 and 112 .
- the third insulating layer 121 may comprise a similar material as the first third insulating layer 111 .
- the third insulating layer 121 may comprise a low-k dielectric material.
- Second vias 21 are formed within the third insulating layer 121 .
- a fourth insulating layer 122 may be formed over the third insulating layer 121 .
- Second metal lines 22 may be formed within the fourth insulating layer 122 .
- a fifth insulating layer 131 is formed over the fourth insulating layer 122 .
- the fifth insulating layer 131 includes third vias 31 disposed within.
- the elements of the resistive switching device are formed in accordance with embodiments of the present invention.
- the resistive switching device is formed above the fifth insulating layer 131 as further described below.
- a first dielectric layer 20 is deposited over the fifth insulating layer 131 .
- a (third) metal line 10 is formed within the first dielectric layer 20 .
- a second dielectric layer 50 is deposited over the first dielectric layer 20 .
- a bottom electrode of the resistive switching device is formed within the second dielectric layer 50 , which may comprise silicon nitride, silicon oxide, TEOS, and others.
- the second dielectric layer 50 may comprise a similar material as the first insulating layer 111 in various embodiments.
- the second dielectric layer 50 may be about 10 nm to about 1000 nm, and about 30 nm to about 50 nm in one case.
- the second dielectric layer 50 may be deposited using a chemical vapor deposition process or a plasma enhanced chemical vapor deposition process.
- the second dielectric layer 50 may be deposited using a plasma vapor deposition (PVD), although in different embodiments, other deposition techniques may be used.
- PVD plasma vapor deposition
- a photo resist layer is deposited over the second dielectric layer 50 .
- the photo resist layer is exposed for openings 35 using a lithographic process.
- the openings 35 expose a top surface of the metal line 10 .
- a barrier layer 30 is deposited on the exposed sidewalls and bottom surface of the openings 35 .
- a polish stop layer may be deposited prior to the deposition of the barrier layer 30 .
- the polish stop layer may be used to stop the subsequent chemical-mechanical polishing process.
- the barrier layer 30 may be deposited using a CVD, PVD, ALD processes or electro-less plating. In various embodiments, the barrier layer 30 may have a thickness of about 5 nm to about 50 nm. In various embodiments, the barrier layer 30 having a thickness of about 5 nm to about 15 nm is deposited.
- the barrier layer 30 is not formed around an upper portion of the sidewalls of the opening 35 . This is accomplished by not forming the barrier layer 30 over a top rim or upper portion of the opening 35 .
- such a structure may be produced in different ways. For example, a conformal barrier liner may be deposited and an upper portion of the conformal barrier liner may be subsequently removed. Alternatively, in another embodiment, the barrier material may not be deposited along the upper sidewall of the opening. In various embodiments, the sidewall angle 41 may be vertical or inclined to enable the formation of such a structure.
- the absence of a small portion of the barrier layer 30 from the rim of the opening 35 has no negative impact on the beneficial effects of the barrier layer 30 .
- the barrier layer 30 may be designed to prevent in-diffusion of metal atoms from the underlying metal line 10 .
- the barrier layer 30 may be configured to promote adhesion with the second dielectric layer 50 .
- the barrier layer 30 may comprise platinum, ruthenium, titanium nitride, tantalum nitride, tungsten nitride, titanium tungsten (TiW), molybdenum, gold, nickel, cobalt, iridium, and combinations thereof, and such other suitable materials used as a barrier material in the semiconductor industry.
- the barrier layer 30 comprises tantalum nitride to prevent copper diffusion from the underlying metal line 10 .
- the barrier layer 30 comprises titanium nitride.
- the barrier layer 30 may comprise an electrochemically inert material (e.g., materials that do not react/diffuse with the switching layer to be deposited subsequently).
- the opening 35 may be filled with a fill material 40 .
- the bottom electrode of a resistive switching may be an electrochemically inert material in one or more embodiments. Therefore, in one embodiment, tungsten (W) may be chosen for this layer. W-plugs may be used as the bottom electrode in one embodiment. Accordingly, the bottom electrode of the resistive switching device comprises a fill material 40 , e.g., comprising tungsten, and a barrier layer 30 .
- the bottom electrode may comprise platinum, ruthenium, titanium nitride, tantalum nitride, titanium tungsten (TiW), molybdenum, gold, nickel, cobalt, iridium, and combinations thereof, and such others.
- the fill material 40 may deposited using a CVD, PVD, or other suitable deposition processes in various embodiments.
- a polishing process may be used to remove the overfilled fill material 40 and optionally any remaining conductive barrier 40 from over the second dielectric layer 50 .
- a chemical-mechanical polishing (CMP) process is used for the planarization process.
- the CMP process may be stopped after removing the fill material 40 and the barrier layer 30 in one embodiment, for example, by using a polish stop layer described above.
- an etch process or a combination of etch and CMP processes may be used instead of the CMP process.
- a third dielectric layer 45 is deposited over the second dielectric layer 50 .
- the third dielectric layer 45 may comprise a same material as the second dielectric layer 50 in one embodiment.
- the third dielectric layer 45 may comprise a silicon nitride layer.
- the third dielectric layer 45 may include silicon di oxide including TEOS oxide, silicon nitride, silicon oxynitride, and other low-k dielectrics.
- the third dielectric layer 45 may be a bilayer in some embodiments.
- a photo resist layer is deposited over the third dielectric layer 45 .
- the photo resist layer is exposed to form openings for switching layer 36 using a lithographic process.
- the openings for switching layer 36 expose a top surface of the fill material 40 .
- a switching layer 60 is deposited within the openings for switching layer 36 .
- the switching layer 60 is deposited over the exposed top surface of the second dielectric layer 50 and the fill material 40 .
- the switching layer 60 may comprise a solid electrolyte layer that provides an ion conducting path capable of forming a conductive bridge.
- the switching layer 60 may comprise a chalcogenide material such as a germanium based chalcogenide, e.g., a copper doped GeS 2 layer.
- the switching layer 60 may comprise silver doped GeS 2 .
- the switching layer may comprise Ge x S y , Ge x Se y , WO 3 , Cu/Cu 2 S, Cu/Ta 2 O 5 , Cu/SiO 2 , Ag/Zn x Cd 1-x S, Cu/Zn x Cd 1-x S, Zn/Zn x Cd 1-x S, GeTe, GST, As—S, Zn x Cd 1-x S, TiO 2 , ZrO 2 , methylsilesquioxane, GdOx, and/or SiO 2 .
- the switching layer 60 may comprise a plurality of layers and may include bilayers such as Ge x Se y /SiO x , Ge x Se y /Ta 2 O 5 , Cu x S/Cu x O, Cu x S/SiO 2 and combinations thereof.
- the switching layer 60 may comprise doped metal oxides such as copper and/or silver doped hafnium oxide, gadolinium oxide, and other such materials.
- the switching layer 60 may comprise transition metal oxides that change conductivity due to the formation of charged point defects such as oxygen vacancies and other charge complexes so as to form a metallic conducting phase.
- the switching layer 60 may comprise metal oxides such as copper and/or silver doped hafnium oxide, gadolinium oxide, and other such materials in various embodiments.
- a metal oxide based switching layer 60 may comprise NiO x , TiO x , Al 2 O 3 , Ta 2 O 5 , CuO x , WO x , CoO, chromium doped perovskite oxides such as SrZrO 3 , (Ba, Sr)TiO 3 , SrTiO 3 , copper doped MoO x , copper doped Al 2 O 3 , copper doped ZrO 2 , Al doped ZnO, Pr 0.7 Ca 0.3 MnO 3 .
- the switching layer 60 may be deposited using a PVD, CVD, PECVD, ALD, and other suitable deposition process.
- the switching layer 60 may be doped during or after the deposition process.
- the switching layer 60 may be doped using a photo-doping process.
- the switching layer 60 may comprise a thin film of GeS 2 deposited by radio frequency (RF) PVD process and a thin layer of electrochemically active metal deposited by DC PVD process.
- RF radio frequency
- electrochemically active metal deposited by DC PVD process.
- this thin layer of electrochemically active metal may be subsequently dissolved into the GeS 2 film using a photo-diffusion process to form a doped GeS 2 layer.
- the switching layer 60 may be formed, e.g., using a deposition process to form WO 3 , Cu/Cu 2 S, Cu/Ta 2 O 5 , Cu/SiO 2 , Ag/Zn x Cd 1-x S, Cu/Zn x Cd 1-x S, Zn/Zn x Cd 1-x S, GeTe, GST, As—S, Zn x Cd 1-x S, TiO 2 , ZrO 2 , SiO 2 .
- a plurality of layers may be deposited, for example, using an atomic layer deposition process to form a stack comprising Ge x Se y /SiO x , Ge x Se y /Ta 2 O 5 , Cu x S/Cu x O, Cu x S/SiO 2 .
- a top electrode layer 70 is formed over the switching layer 60 .
- the top electrode layer 70 may comprise an electrochemically active metal such as silver, copper, zinc, and others in various embodiments.
- the top electrode layer 70 may be deposited using a sputtering process, a vapor deposition process such as a physical vapor deposition process, chemical vapor deposition process, plasma enhanced chemical vapor deposition process, an atomic layer deposition process, and other processes.
- An optional capping layer 75 may be formed over the top electrode layer 70 .
- the capping layer 75 may comprise titanium nitride or tantalum nitride (as well as other suitable materials) in various embodiments.
- the capping layer 75 may be deposited in one or more embodiments using sputtering or other vapor deposition processes.
- the switching layer 60 , the top electrode layer 70 , and the capping layer 75 may be deposited without breaking vacuum, for example, using a cluster tool, which may be a PVD tool in one embodiment.
- the bottom electrode contacting the switching layer 60 comprises a top surface having the same material. Unlike FIG. 1 , which has two types of materials forming the top surface of the bottom electrode, in FIG. 2 , only the fill material 40 contacts the switching layer 60 .
- FIG. 3 which includes FIGS. 3A and 3B , illustrates embodiments in which one of the top surface of the bottom electrode of the resistive switching device is deactivated or does not participate in the electrical operation of the device.
- the resistive switching device is formed between the barrier layer 30 and the switching layer 60 .
- An additional cap layer 55 which may be a dielectric layer, may be formed over the fill material 40 . Consequently, the fill material 40 is separated from the switching layer 60 by the cap layer 55 .
- the cap layer 55 may comprise a dielectric layer to prevent electrical contact between the fill material 40 and the switching layer 60 .
- the cap layer 55 may deactivate the fill material 40 from participating in the switching action by changing the potential drop through the switching layer 60 and/or by cutting the flow of current. For example, the potential drop across the switching layer 60 between the capping layer 55 and the top electrode 70 may be smaller than the voltage drop across the switching layer 60 between the barrier layer 30 and the top electrode 70 .
- the cap layer 55 may comprise low-k dielectric material (dielectric permittivity less than silicon oxide) to further minimize the capacitive effects.
- the cap layer 55 may also be selected to minimize leakage currents due to tunneling of carriers from the fill material 40 and the switching layer 60 in various embodiments. Consequently, in one or more embodiments, the cap layer 55 may comprise a dielectric layer having an effective electrical thickness greater than 5 nm, e.g., silicon dioxide layer having a thickness of at least 5 nm or a silicon nitride having a thickness of at least 25 nm.
- FIG. 3B illustrates an alternative embodiment in which the resistive switching device is formed between the fill material 40 and the switching layer 60 .
- an additional cap layer 55 may be formed over the barrier layer 30 .
- the cap layer 55 may be a dielectric material having an effective electrical thickness greater than 5 nm, e.g., silicon dioxide layer having a thickness of at least 5 nm or a silicon nitride having a thickness of at least 25 nm.
- the switching layer 60 contacts the fill material 40 without contacting the barrier layer 30 .
- FIG. 4 illustrates an alternative embodiment of a resistive switching device comprising a barrier layer 30 and a switching layer 60 .
- the first distance H 1 is smaller than the second distance H 2 , which may be suitably adjusted. Therefore, the potential across the first distance H 1 between the barrier layer 30 and the top electrode is larger than the potential drop across the second distance H 2 between the fill material 40 and the top electrode 70 . Accordingly, the conductive pathway of the low resistance state of the resistive switching device forms primarily over the barrier layer 30 . Accordingly, in this embodiment, the surface properties of the fill material 40 are made to be less important relative to the surface properties of the barrier layer 30 .
- FIG. 5 illustrates a resistive switching device in accordance with an alternative embodiment of the present invention.
- FIG. 5 refers to one embodiment of forming a structure similar to that of FIG. 2 .
- the opening 35 for the bottom electrode may be tailored or angled in one or more embodiments so that the material of the barrier layer 30 may not deposit over the rim portion of the opening 35 during subsequent deposition.
- the sidewall angle 41 may be less than 90°, for example about 70° to about 90°, and about 80° to about 85° in one embodiment.
- the deposition of the barrier layer 30 may be controlled to achieve a similar effect.
- the deposition direction may be angled in a directional deposition technique such as sputter deposition.
- the wafer carrier holding the wafer
- the wafer may be angled and rotated during deposition.
- the wafer may be tilted by about 5° to about 25°, and about 1° to about 5° in another embodiment.
- the chuck carrying the wafer may be rotated continuously or in steps (e.g., 45°, 90°, 135° etc.).
- Embodiments of the invention also include combinations of the above.
- the profile and coverage of the barrier layer 30 may also be controlled by various deposition process adjustments including variations in bias power, source power, pressure, gas flow rate and/or temperature.
- a thick barrier layer 30 is formed on the bottom surface of the opening 35 as illustrated in FIG. 5 .
- the fill material 40 is deposited and a chemical mechanical planarizing (CMP) may be performed to planarize the structure thereby forming a structure similar to FIG. 2B . Subsequent processing may follow as described with respect to FIG. 2 .
- CMP chemical mechanical planarizing
- Embodiments of the invention also include deactivating the barrier layer 30 so that the top surface of the barrier layer 30 may not take part in the operations of the resistive switching device.
- An embodiment of such a method will be described using FIG. 6 , which includes FIGS. 6A-6D .
- FIG. 6 which includes FIGS. 6A-6D , illustrates a resistive switching device during various states of fabrication, wherein the top surfaces are selectively modified.
- FIGS. 6C and 6D illustrate alternative embodiments. This method may be used to form the structure illustrated in FIG. 3A or 3 B in one embodiment.
- the barrier layer 30 and the fill material 40 may be formed within the opening 35 as described previously.
- the exposed top surfaces of the barrier layer 30 and the fill material 40 are subjected to a treatment.
- the treatment is configured to selectively react with one or both barrier layer 30 and the fill material 40 .
- the treatment may be a chemical, physical surface treatment and may also include exposing the surfaces to a plasma in some embodiments.
- the treatment may be an oxidation process that oxidizes both the barrier layer 30 and the fill material 40 ( FIG. 6B ).
- the barrier layer 30 may oxidize and form a dielectric material layer 31 (similar to the cap layer 55 in FIG. 3B ) while the fill material 40 may form a different fill material oxide 32 .
- the oxide of the fill material 40 may be subsequently removed, e.g., using a selective etch process without removing the oxide of the barrier layer 30 .
- a selective etch process without removing the oxide of the barrier layer 30 .
- the barrier layer 30 comprises TiN
- a titanium di oxide dielectric layer is formed over the barrier layer 30
- the fill material 40 comprises tungsten
- a tungsten oxide is formed over the fill material 40 .
- the tungsten oxide may be dissolved/etched using water, dilute hydrofluoric acid and such others without etching the titanium oxide.
- the oxide of the barrier layer 30 may be selectively removed without removing the oxide of the fill material 40 .
- selective reaction with the barrier layer 30 or the fill material 40 may create the final structure without the need for the etch process.
- FIG. 7 which includes FIGS. 7A-7D , illustrates an alternative embodiment of the invention for forming the structure illustrated in FIG. 2 .
- the barrier layer 30 is first formed within an opening 35 .
- an angled etch is used to remove the outer rim of the barrier layer 30 .
- the angling may be obtained by either tilting the substrate (e.g., the wafer) or the etch species is angled relative to the substrate.
- the wafer or etch species angle may be rotated (as in FIGS. 7B and 7C ) to remove the barrier layer 30 uniformly from the upper sidewall of the opening 35 .
- Subsequent processing may form a structure as shown in FIG. 2A .
- an additional insulator may be deposited in some embodiments, or a different metal may be deposited.
- a thin layer of fill material 42 e.g., tungsten layer
- the thin layer of fill material 42 may be about 10 nm to about 50 nm in one embodiment and may be formed as a conformal layer.
- the PVD process provides excellent adhesion and avoids crack/delamination between the bottom electrode and the second dielectric material layer 50 .
- the fill material 40 may be deposited using a chemical vapor deposition process.
- both the thin layer of fill material 42 and the fill material 40 are the same material and therefore there are no issues arising from differences in work function or other electronic properties.
- FIG. 8 which includes FIGS. 8A-8H , illustrates a resistive switching device during fabrication in accordance with various embodiments of the invention.
- the final structure of the inert electrode may be similar to the embodiment described in FIG. 2 .
- an opening 35 is formed within the second dielectric layer 50 .
- the opening 35 may be formed over a metal line 10 as described previously. Additional layers underneath the second dielectric layer 50 are not shown for clarity.
- FIG. 8B illustrates the resistive switching device after the deposition of a liner.
- the liner may comprise the barrier layer 30 in various embodiments.
- a dummy material 51 is deposited within the opening 35 .
- the dummy material 51 may be a photo resist material or an anti-reflective coating such as a bottom anti-reflective coating (BARC) layer in an alternative embodiment.
- BARC bottom anti-reflective coating
- the dummy material 51 may comprise any suitable material that is easily removed from within the opening 35 without significantly removing the second dielectric layer 50 or the barrier layer 30 .
- the dummy material 51 may be applied using a coating process in one or more embodiments.
- the dummy material 51 After forming the dummy material 51 , a portion of the dummy material 51 is removed as illustrated in FIG. 8D .
- the dummy material 51 is subjected to an etching process, which may be timed to achieve a certain fill height as in FIG. 8D .
- the dummy material 51 may be partially filled during the forming of the dummy material 51 (instead of overfilling followed by an etch back) so as to directly form the structure illustrated in FIG. 8D .
- the partial fill by the dummy material 51 exposes an upper portion of the liner material.
- the exposed liner is next removed thereby forming the structure illustrated in FIG. 8E .
- a single etching process may remove both the dummy material 51 and the liner thereby skipping the structure illustrated in FIG. 8D .
- the etching of the dummy material 51 and the exposed liner may be performed within a single multi-chamber cluster tool, e.g., without breaking vacuum.
- the dummy material 51 is removed, for example, a resist strip process may be used.
- a wet etching process may be used in one or more embodiments.
- the fill material 40 is deposited within the opening 35 .
- the fill material 40 is overfilled as illustrated in FIG. 8G .
- the overfill may be removed using a planarization process to form the structure illustrated in FIG. 8H .
- any cracks formed between the upper sidewalls of the opening 35 and the fill material 40 may also be removed during the planarization (due to thinning).
- the fill material 40 may be deposited in at least two steps. As illustrated in FIG. 8G , first, using a first deposition process, e.g., a PVD process, a thin layer of fill material 42 is formed, for example, using a conformal deposition process. Then, using a second deposition process, e.g., a CVD process, the fill material 40 is deposited.
- the multiple step deposition process may be used to ensure good adhesion between the fill material 40 and the sidewalls of the opening 35 .
- FIG. 9 which includes FIGS. 9A and 9B , describes an alternative resistive switching device during various stages of fabrication in accordance with an embodiment of the invention.
- the bottom electrode comprises a first portion and a second portion.
- the second portion of the bottom electrode may be formed using conventional processing. Consequently, a barrier layer 30 and a fill material 40 are formed to form a second portion of the bottom electrode. However, as will be described, over this second portion, the first portion is formed. As will be described, the first portion contacts the switching layer 60 of the resistive switching device.
- a liner 150 e.g., an etch stop liner, is deposited over the second dielectric layer 50 , the barrier layer 30 , and the fill material 40 .
- a fourth dielectric layer 160 is deposited over the liner 150 .
- An electrode opening 135 is formed within the fourth dielectric layer 160 .
- the electrode opening 135 may also extend through the liner 150 thereby exposing the top surfaces of the barrier layer 30 and the fill material 40 .
- the electrode opening 135 within the fourth dielectric layer 160 is filled with a second fill material 140 , e.g., tungsten.
- a second fill material 140 e.g., tungsten.
- the bottom surface of the second fill material 140 contacts the top surface of the fill material 40 .
- the second fill material 140 and the fill material 40 do not interact.
- the top surface of the second fill material 140 does not include a chemically active species, for example, any non-inert atoms from the fill material 40 or the barrier layer 30 .
- the same material is deposited (e.g., tungsten over a prior tungsten layer)
- no additional barrier layer is required between the first fill material 40 and the second fill material 140 .
- any resistive memory such as a resistive metal oxide memory, phase change memory, resistive random access memory, conductive bridging random access memory, and others.
- resistive memories such as phase change memories, nano-conductive bridge memories may be formed above (and contacting) the inert electrode formed from the fill material 40 as described in various embodiments of FIGS. 2-9 .
- other types of memories including other types of resistive memories, ferroelectric memory, and others may be formed above (and contacting) the inert electrode formed from the fill material 40 as described in various embodiments of FIGS. 2-9 .
- other types of devices such as a one time programmable devices, a field-programmable gate array devices may be formed above (and contacting) the inert electrode comprising the fill material 40 as described in various embodiments of FIGS. 2-9 .
Abstract
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